Production of higher ketones



Patented Dec. 15,1936

UNITED STATES PATENT OFFICE PRODUCTION OF means. xnrroNns om Fuchs,Frankiort-on-the-Main, nrlchmn joks, Berlin-Zehlendori' Mitte, andWilhelm Querfurth, Mainz-Mombach, Germany No Drawing. Application April3, 1935, semi No. 15,134. In Germany August 19, 1931 15 Claim.

with alcohols having an aliphatic character such,

as aliphatic alcohols or .alicyclic alcohols. The ketones involved havean aliphatic character such as aliphatic or alicyclic ketones.

We have foundthat, starting from low ketones,

e. g. acetone, methyl ethyl ketone, etc., higher ketonesare readilyproduced by effecting a direst alkylation of such low ketones by theaction of aliphatic alcohols in the presence of catalysts. In thepresent process alkyl groups are introduced' directly, that.is, withoutthe use of an oxygen atom into the molecule. oi. the ketone.

The newly introduced alkyl groups are those combined with the ketonemolecule ,through a direct carbon to carbon (CC) linkage. Such ketonesproduced by the O--C alkylization are briefly called higher ketones inthe present application, and such term is to be so understood also inthe claims hereinafter. proceed in a clear manner and with satisfactoryyields in the sense of the following equations for example:

Elevated temperatures-e. g. 150 C. to 400 C.and the presence ofcatalysts are necessary for carrying out the reaction. The followingcatalysts, for example, have proved to be useful: 7

4o magnesia or aluminium oxide in a sufllciently active iorm asprincipal constituents, to which are added certain quantities ofcatalytically active metals-e. g. copper or both copper and silverq-orof metallic oxides or carbonates of 45 known catalytic activity-forexample, barium 1 oxide or molybdenum trioxide or both. v

The reaction may be carried out by continuously passing the vapors ofthe ketone and the aliphatic alcohol in the gaseous phase under ordinaryor increased pressure over the catalyst,

but it is also possible, particularly when working The conversions thedesorption of the formed higher ketones from the catalyst.

According to the nature of'the catalyst and to the temperature, otherconversions can occur to a certain extent-e. g. the formation of higheralcohols from ethyl alcohol-in accordance with the following equationsIn a similar manner, by the action of hydrogen upon the ketones,thecorrespoziding secondary alcohol can be produced in smallquantities-for example, isopropyl alcohol from. acetone. Further, suchketones as are produced by condensation of ketones with branched chainsmay be tormede. g. methyl isobutyl ketone irom'acetone through mesityloxide. Nevertheless, by choosing the experimental conditions, it ispossible to force such secondary reactions, it they are not desired,entirely into the background. In certain circumstances it may be usefulto take advantage of secondary reactions and to employ the resultingmixtures as such-e. g. as solvents ,or to subject them to a'tworking upwhich involvesno difliculty, becausewe have here a mixture oi.chemically well defined substances. It is, inter alia, easily possibleto separate the alcohols Irom the ketones by esteriflcation for example.

Also, mixtures of ketones with the esteriflcation products or thealcohols for example, acetic acid esters, constitute extremely valuablesolvents.

To the extent to which the initial product's, namely, ketone andaliphatic alcohol, come out oi. the reaction unchanged, they may beseparated, for example by distillation, and again subjected toconversion.

The mixed catalysts involved in the present process are those whose onecomponent has a dehydrogenizing action (splitting oft-H) and the other adehydrating 'action (splitting oil H20). The first group,- namely thehydrogenizing type, comprises as is known, copper, zinc, zinc oxide,cadmium, tin oxide, vanadium oxide, bismuth, chromuim, oxide, molybdenumoxide, uranium oxide, managanese oxide, iron, nickel, platinum, etc.and/or their carbonates, iormates, etc. The catalyst components of thedehydrating type with the water splitting action comprise, as is known,

catalysts and contain at least one representative -from each of thesetwo groups, namely the de-.

hydrogenizing group and the dehydrating group. The above mentionedcatalysts may be replaced the earth alkali metals, earth metals, rareearths,

.by other mixed catalysts with equal eueeeee. The

mixed catalysts in question consist advantageously of a component whichprimarily has a watersplitting (dehydrating) action, and of componentswhich have hydrogenating properties. Water-splitting componentscomprise: magnesium, aluminum, beryllium, boron, titanium, zirconium,cerium, thorium, oxides, hydroxides, canbonates or salts(nitrateahcetates) thereof. The

magnesium may be replaced by calcium, barium or; zinc oroxygen-containing compounds thereof,

such as carbonates, hydroxides, etc. This group also comprises carbon,e. g. wood charcoal, active carbon, coke, and also silicic acid,preferably in the form of silica gel. illlie aforementioned substancesor their cbmpounds may be used severally" or in admixture with eachother.

The hydrogenating catalyst components comprise: copper, manganese,silver, chromium, nickel, tungsten, cobalt, iron, cadmium, uranium,thorium lead, tin and zinc. These substances may be used as metals or inthe form oftheir oxides, hydroxides, carbonates, acetates, nitrates, orin the form of other salts, and also as complex salts. These substancesor' their compounds may be used severallyor in admixture with eachother.

The reaction maybe carried out at ordinary as well as at elevatedpressure (e. 'g. 30-100 atm.).

Example 1.-The catalyst is produced by im-' .pregnating activealuminawith 15 per cent ofcopper formate and 1.8 per-cent of molybdenumtrioxide and then treating the impregnated -alumina with a mixture ofair'and steam at 450 0. Methyl alcohol and acetone in equlmolecularquantities at 230 C. with the employment of nitrogen as a diluting gas,are passed over the catalyst. The water ampuntlng to 20.6 per ,cent

is removed from the condensate by drying with potassium carbonate. Theworking up' of the product by fractionation at a barometric pressure of730 mm. gives the following result:

5 7 Per cent Up to .60" C 17.4 ir'rom 60 to 70 C 9.8 From'70 to C 27.9From 80'to 105 0 "i 4.1 From 105 to 120 c 5.0 Above 120 a Water (removedby preliminarydrylng as above stated) 20.6

The analysis of the individual .meuem gives If the molybdenum trioxideis replaced by the equivalent quantity of barium oxide, the convercarbonis leftin the form of unchanged initial slon; is improved .and only28;,per cent of the substancesi'l-Thequantity of polysubstituted high-centages of metal is Mg:AltCu=89:8:3.

boiling -ketones is correspondingly in- Emmple 2.'1echni cal magnesiumoxide is thoroughly kneaded with an aluminium-hydroxide Jelly, copperoxide and silveroxide in such quantities that the composition calculatedon percentages-of metal is Mg:A l:Cu:Ag=89 :8:2:1

A, quantity of acetone and 04 per cent ethyl alcohol in equal weights ispassed together with hydrogen at 200 C. over the catalyst which has beendried and pretreated with a mixture of air and steam. Calculated onparts of carbon in the initial material as basis, 18 parts are recoveredas acetone and 31 parts as ethyl alcohol,

while 18 parts are obtained as methyl propyl ketone, over 4 partsas'dipropyl ketone and a further 4 parts asketones having a still higherboiling point. In addition, butyl and hexyl alcohol (together about 10per cent) and some ethyl acetate'(2 per cent) are produced in smallerquantitles as secondary products.

11, instead of -the above mentioned catalyst, activated alumina that isimpregnated with copper formate (5 per cent of metallic copper) isemployed, and the operationds carried out at 260 0., very similarrolultsare obtained. A part of the unused ethyl alcohol occurs in the form ofacetaldehyde which can again be used as such as initial material for thereaction, since it replaces the ethyl alcohol in equivalent quantity.Example 3.-Commercial maznw um oxide is worked up with aluminiumhydroxide and copper oxide imsuch quantities that the ratio of the per-The catalyst, which is dried and comminuted to the .sise of peas, istreated in an iron contact tube with air and steam at 400 to 500' C. andthereupon'a mixture of 3.0 mols of acetone, 2.5 mols of ofliyi alcoholand 3.2 mols of hydrogen is passed over thecatalyst under apressure of30 atmospheres and at a temperature of 231' c. The ethylalcoholusedisofastrengthofflpercent by weight. The boiling-pointanalysis of the combined and dried products of the reaction at apressure of 730 ms. of mercury gives the followin: result-:-

' Gms. Up to 50' c as so to 65 D 421 s5 to 85 862 as to r' 248 105 to 0its 130 to 0 181 170 to 200' o 120. Above 2005 c 85 The result of theworking up is that, calculated on percentages of carbon, the product ofthe reaction contains 62 per cent in the form of unused ethyl alcoholand acetone, 5 per cent of the fraction to be reckoned as ethyl alcoholbeing present as aldehyde. Further, 18 per cent'of the carbon is presentas methyl propyl ketone and 9 per cent as dipropyl ketone. Higheralcoholscan be isolated in smaller quantities-i. e. 5 per cent ofthecarbon as butyl alcohol, 7 per cent} as hexyl- 1 alcohol and higheralcohols. The mixture of acetaldehyde, acetone and ethyl alcohol canagain be supplkd to the reaction. 3

In the cataylstsused, the copper fraction may be replaced by otherhydrogenating or metallichompounds, e. g'. zinc orvanadium oxide ornickel; similarly, the fraction may be replaced by barium or calcium orsilica gel, etc.

There is no quantitative or qualitative difference in the yield.

Example 4.A mixture of 2.5 mols of acetone. 2.0 mols oi butyl alcoholand 3.0 mols of hydrogen is passed, under a pressure of 30 atmospheresand at a temperature ot-354 C., over the catalyst employed in Example 3;The boiling point analysis at a pressure or 730 ms. of mercury givesGirls. 50 to 65 C 536 65 to 90 C 210 90 to 130 C 2'73 130 to 170 C 1034170 to 200 C 107 Above 200 C 665 The main quantities of the individualfractions pass over within a few degrees, the principal product of thereaction-namely, methyl amyl ketone-ior example, passing over at 150 C.By

further working up and analysis of the individual fractions, thefollowing result is obtained for Q 2 every 100' parts of carbon in themixtures- Parts As unchanged acetone 15.0 As isopl'opyl alcohol 4.9 Asunchanged butyl alcohol 6.2 As methyl amyl ketone 29.0

As heptyl'alcohol (mainly probably heptanol-2) 2 Ashigher ketones andalcohols, the main quantity being .diamyl ketone 23.1

The remaining 14.5 parts are attributed to losses in the reaction and.in the working up, and to products not-found in the anaylsis.

. Ii somewhat lower reaction temperatures-e. g. 319 C.are employed, theconversion into the higher boiling point products is smaller and for;

example, methyl amyl ketone as the preferred reaction product isobtained in an amount higher than 60 per cent oi. the fractions boilabove the boiling point oi'the butyl alcohol.

Example 5.--A mixture of 2 mols of methyl ethyl ketone, 3 mols of ethylalcohol and 3 mols or hydrogen is passed, under a pressure of 30atmospheres and at a temperature of 317 C., over the same catalyst asthat employed in Examples P 3 and 4. The working up of the reactionproducts, after separating oil the unchanged initial substancesincluding a little acetaldehyde, which was produced from the ethylalcohol, and some butanol-2, which was produced from the ketone, showsthat, of the carbon present 26 per cent is present as Ca-ketones, 11 percent as Caketones and 4 per cent as ketones boiling above 200 'C. Inaddition, higher alcohols are produced: 31 per cent 01 the carbon isfound as n-butyl alcohol, 14 per cent as hexylalcohol and 'a iurther 14per cent as higher alcohols.

II higher reaction temperatures-e. g. 351 C.- are employed, the quantityof ketones boiling above 200 C.'is considerably increased. Thi s.

for example, from 100 parts of carbon, there are obtained about 10 percent eachoi Cs-ketones and Cakt0nes and above 50 per cent as ketonesboiling above 200 C.'mixed with some higher. alcohols.

Example 6.The operation is carried out at 250-300? in reaction tubesmade-of almninum or iron. Part of .the experiments were carried out atelevated pressure (30 atm.) and part at ordinary pressure. Severaltests'with aeetoneand butanol as initial material were carried out inthe liquid phase. Use was made at an iron pressure tube of 500 cc.capacity. The catalyst which was used had a grainsize oi mm. andcontained Mg 89, Al '8, and Cu 3 mol. as metal. Rate at movementamountedto 1.3 mols acetone-+1.7 mols glycol+3.2 mols H: per hour and 1 litercontact. Operative pressure was 30 atm.

and the operative period was 3x24 hours. When the action or the contactappeared about to Upon elimination of two mols of water,.diacetylbutanei'orms with 2 mols of acetone, B. P. 114.

Example 7.Use was made of a pressure tube.

The contact consisted of Mg 89, Al 8, Cu 3. The

rate oi passage was 2.5 mols acetone,+1.5 mols hexanol=3 mols H: perhour and liter contact. The operative pressure was atm. and theoperative period was 6x24 hours. Herealso, as in Example 6, the catalystmay be regenerated. Used: 10300 g. acetone+10640 g'. hexancl= 20940 3.mixture. Obtained-z Up o-w GINO acetaldeliyde 50- 05 2351 acetonetraction (wash column) 65- 86 506 Iropropyl fraction 85-- 06 2130isopl'opyl traction Aceotropicallv dehydrated 50- 86 2004 hcxyl traction1 86-135 2370 metbylbeptylkotone traction figkiheptylkatone traction15184 Reaction product obtained: 72.5% of the mixture used. 2,286 g. ofdiheptyl fraction-were obtained containing about diheptylketone. The2700 g. or methylheptylketone traction contained 47%.01methylheptylketone. The B. P. of

methylheptylketone at ordinary pressure is 194-196. At 24 mm., it isabout 100. ketoneboils at 1'78-at 20 mm.

. Example 8.-'Use was made of a'pressure tube.

Diheptyl- The contact consisted of -Mg 89,. Al 8 and Cu .3.

The rate of passage was 2mols butanol+2.5 mols acetone+3 mols Ha perhour and liter contact. The operative period amounted to 24 hours andsubsequentpxidation. The temperature was 350. In mol. C ottheusedmixture:

Acetone 15.0 Iscpropyl 4.9- Butanol 6.2 See. heptyl 4."lMethylamylketone 29.0 See. Cn-alcoh 2.6

Diamyl ketone----..-. 23.1

Methylpropyl ketone (13. P.-102), contained Residue drogenated,resulting in'a 99.8% carbinol, which' distills well. MethylamylketoneB.P. 740 152,

carbinol B. P. 157. Dlamylketone B. P. 740 227', carbinol B. P. 8 104. Y

An operative test was carried out with the 'same contactfor an operativeperiod or 3x48 hours at 30 atm. in the iron tube. The above outlinedtest was confirmed in the liter ca .pacity reaction tube, thus assuringthat the present process can also be carried out on a large scale.

Further tests in the liquid phase with the same contact also confirmedthis possibility.

Example 9.-This test was carried out at about 260 at ordinarytemperature in the aluminum tube at 24 hour intervals, with interposedoxidation, the rate of flow being 0.5 mol. ethanol+0.4 mol. acetone+1.5mols K: per hour and liter contact. Obtained, in moi. C of the usedmixture: approx. methylpropyl ketone and 5% dipropyl ketone. The contactcoimisted oi Mg-89, A1 8, Cu 2, Ag 1.

Under the same conditions, with the contact Al I (Cu 5)with activealumina impregnated with copper iormate-there were obtained 15% meth- Anoperative test at high pressure at about 300 and atm. in the 10 literiron tube and at a rate of passage of 3 mols ethanol+2.4 mols acetone+3mols H: per hour and liter contact gave the following: a

Used: 233 kg. acetone+212 kg. ethanol=445 kg.

mixture.

Obtained:

Kilogram 'Acetyldehyde 9.0 Acetone 72.9 Ethanol-hiscpropyl 144.4

Recovery=51% oi the used mixture 226.9 Converted=218 kg.-mixture.

Kilogram for the most part in the recovered) spirit 27.7 Methylpropylcarbinol (18.- P. 119) in fraction 110-1302 Dipropyl ketone (B. P. 144')in ilfraction- 130--160 Dipropyl carbinol (B. P. 153) in fractionISO-V10 75 The contact used in this test contained Mg 89, A] 8, C11 3- cc I I Eaample 10.The rate of passage was 1 mol. admixture-in theproportion 1:1 per liter contact and hour, nitrogen .being used as adiluent. The

a contact was Al (Cu 9 Mo 1);'-the temperature was 230 at ordinarypressure. Obtained: 22% methylethyl ketone and 16.4% diethyl keamass.tone-i-isobutyl-methyl ketone. The. aluminum in ,the catalystconstituted 90 to 95% thereof.

Another contact Al (Cu- 9 Ba 1), at a double rate of speed, i. e. 2 molsper hour and liter contact-gave 18.5% methylethyl keto'ne and 2.3-.

2% higher ketones. The aluminum in the catalyst constituted 90 to'95%thereof.

Example 11.-'Ihe,. test was; carried outwith about 2 mols acetone+2molsbutanol+3 mols hydrogen per hour and liter contact at 320 and 30 atm..The admixture was passed over the contact in a stationary, electricallyheated tube of 0.5 liter capacity. The grain size oi. the contact was5-8 mm.

Al, (Cu'4 Be %)--active aluminum oxide.

impregnatedwith a solution of copper formate and beryllium acetate. Thealuminum present constituted 90 to 95% of the catalyst.

Used: 32.34molsCin4hours Recovered: 11.64 mols C- (acetone, isopropyl,

butanol) Converted: 20.70 mols C63.8% or the used C.

Obtained:

UM I (m- Pereent Permit Example 12.This test was carried out under thesame conditions aaJest 11. Mg88Al6%Cu51"e%(C5P20)-a contact obtained byadmixing the commercial oxides or sawdust and phosphoric acid- Used:29.40 mols C in 4 hours Recovered: 12.40. mols O (acetone, isopropyl,

butanol) Converted: 17.0 mols 0:57.898 of the used 0.

' (95 d. Tb Ulil 0 con Poul Pa'uat 14. 1 7. 8 C. 1 l0. 5 7. 8 12. 0 0 0Y 5. 0 9. e 1: 4 "2. 4 0. 4 0. 9

' 37. 0 63. 9 Recovered 42. 2

Total 79. 2 Hydrocarbons and losses 2o. 8

It is desired toxpoint out that the above men; tioned catalysts in thevarious examples may be replaced by other mixed catalysts with equalsuc-- cess. As was pointed out above, the mixed catalysts consistadvantageously of a component which has a dehydrating action and acomponent i which has a hydrogenating property. Such catalysts have beenset forth in detail previously.

The present process relates to the treatment of ketones, on the onehand, with aliphatic alcohols, on the other; The ketones involvedcomprise acetates. methylethyl kctone. diethyl ketone.

methylpropyl ketone and the higher homologues, such as diamyl ketone anddiheptyl ketone. Alicyclic ketones, such as acetophenol, phenylethyhketone, may also be reacted in similar manner. The-reaction may becarried out in the vapor phase or in the liquid phase. The operation mayalso be eflected in the presence of diluents, such as nitrogen, carbondioxide or hydrogen, as well as in the presence of inert liquid diluents(insofar as the reaction is carried out in the liquid phase).

With respect to the proportions between the dehydrating component andthe hydrogenating. component of the catalyst itis preferable that the Adehydrating component be greater than the hydrogenating component.

In the following claims the term aliphatic includes. both aliphatic andalicyclic ketones and also aliphatic and alicyclic alcohols such forinstance as benzyl alcohol or phenylethyl alcohol.

We claim:

1. The method of producing higher ketones comprising contacting analcohol having an allphatic character with a lower ketone in thepresence of a mixed-catalyst comprising essentially hydrogenating anddehydrating-components at a temperature between 150 and 400 C.

2. The method of producing higher. ketones comprising contacting analiphatic alcohol with a lower ketone in the presence of a mixedcatalyst comprising essentially hydrogenating and dehydrating componentsat a temperature between 150 and 400 C.

3. The method of producing higher ketones comprising contacting analiphatic alcohol with i a lower ketone in the vapor phasein thepresence Gil of a mixed catalyst comprising essentially hydrogenatingand dehydrating components at a temperature between 150 and400 C. p

' 4. The method of producing higher ketones comprising reacting analiphatic alcohol with a lower ketone in the vapor phase in the presenceof a mixed catalyst comprising essentially hydrogenating and dehydratingcomponents and a dilueng inert gas at a temperature between 150 and 40C.

5. The method of producing higher ketones comprising contacting analiphatic alcohol with a lower ketone in the vapor phase in the presenceof hydrogen and a mixed catalyst comprising essentially hydrogenatingand dehydrating components at a temperature between 150 and 400 C.

6. The method of producing higher ketones I comprising reacting analiphatic alcohol with a 8. The method of producing higher ketone?comprising reacting an aliphatic alcohol with a lower ketone in thepresence of a catalyst comprising essentially an alkaline earth metaloxide as the main constituent and a hydrogenating f catalyst taken froma group consisting'oi coper, manganese, silver, chromium, nickel,tungsten, cobalt, iron,"cadmium, uranium, thorium, lead, tin, zinc,barium, molybdenum, vanadium, bismuth, platinum and their compounds as asubsidiary constituent at a temperature between 150 and 400 C.

9. The method of producing higherketones comprising reacting analiphatic alcohol with a lower ketone in the presence of a catalystcomprising essentially an earth metal oxide as the mainr constituent-anda hydrogenating catalyst taken irom' a group consisting 01 copper,manga'nese, silver, chromium, nickel. tungsten, co-

balt, iron, cadmium, uranium, thorium, lead, tin, zinc, barium,.molybdenum, vanadium, bismuth, platinum and their compounds asavsubsidiary constituent at a temperature between 150 andcomprisingreacting ahigher aliphatic alcohol with a lower ketone at a temperaturebetween 150 and 400 C. in the presence of a catalyst comprisingessentially alumina and magnesium oxide as the main constituents and asmall proportion of copper oxide. g

12. The method of producing higher ketones comprising reacting analiphatic alcohol with a lower ketone at a temperature between 150 and400 C. in the presence of a catalyst comprising essentially aluminaandmagnesium oxide as the main constituents and a small proportion oisilveroxide.

13. The method of producing higher ketones comprising reacting analiphatic alcohol with a lower ketone in the presence of a catalystcomprising essentially alumina and magnesium oxide as the mainconstituents and a small proportion of copper and silver oxides at atemperature between 150 and 400C.

14. The method of producing higher ketones comprising contacting analcohol having an aliphatic character with a lower ketone in thepresence of a mixed catalyst having a dehydrating and hydrogenatingeffect.

15. The method of producing higher ketones comprising contacting analcohol having an aliphatic character with a lower ketone in thepresence of a mixed catalyst comprising a dehydrating catalyst takenfrom' a group consisting or magnesia, aluminium, beryllium, boron,chromium, titanium, zirconium, cerium, thorium,

calcium, barium, silicon, uranium, rare earths and compounds of saidmetals and a hydrogenating catalyst taken from a group consisting ofcopper, manganese, silver, chromium, nickel,

tungsten, cobalt, iron, cadmium, uranium,

thorium, lead, tin. zinc, barium, molybdenum,

vanadium, bismuth, platinum and their compounds. OTTO FUCHS.

ERICH NAUJOKS.

WILI-IELM QUERFURTH.

